DE1646249A1 - Transparent laminate - Google Patents

Description

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DR. E. WIEGAND DIPL-ING. W. NIEMANN DR. M. KOHLER DIPL-INa C GERNHARDT

MÖNCHEN HAMBURG

phone: 55547ί 8000 MDNCHen.15, May 16, 196 ^r

TELEGRAMS: KARPATENT NUSSBAUMSTRASSE 10

W 12 335 / '£ 5 Dr ₀ Ko M 44 059 Vlb / 15 1 Tr

Monsanto Company
Stο Louis, Missouri (Y ₀ St ₀ A ₀ J

■ ■: .'- ■■ ^: I

Transparent laminate (separation from patent application M 44 059 Vlb / 15 I). _

The invention is concerned with the introduction of protective and decorative means in faceplates, comprising a sheet or sheet of plasticized polyvinyl butyral with a Glass plate or a plate of a usable translucent or transparent material combined into a laminate, which at the same time or afterwards with a cover layer can be provided that; serves to avoid a scratch or the ™ Absorption of moisture through the polyvinyl butyral intermediate layer to prevent*

The polyvinyl butyral intermediate layer can be printed by looking at these different inks and preferably those inks that are in polyvinyl butyral are diffusible, ^ by coating or according to others

10983 4 / 001S

BADORLGiNAL

Surface application operations applied to induce a decoration or additional protection against the passage of heat and light by the resulting plates "If, for _o B _o takes a low pressure, the selected color of the cylinders or printing plates, the presses on the surface of the polyvinylbutyral transferred, on which a drawing is created that corresponds to the corrugation or etching on the printing rollers or plates. In order to allow the color to diffuse into the polyvinyl butyral sheets and to achieve a more uniform color effect, the sheets are subjected to a color diffusion stage, whereby they are usually at a temperature of 20 to 6O ⁰ G for one . ' Period of time between 3 to 60 days,

The above process was completely successful _o in creating effective light absorbing media in the areas ■ taken laminates to incorporation of a heat- or light-reflecting layer may be used in which metallic pigments, but was in the laminates, a special or additional operation by the use of vacuum or Other metal deposition techniques may be required. Here, an absorbent medium or layer that is effective on one surface of the laminate and a reflective medium or layer that is effective on the opposite side

BATH

present-ict ₉ e ^ altan werüezu '"The laminated fabrics then know vorc-rbsitet tmd, s _a 3. in!« all- vö & V / inaGcliutz discs with the reflective licit «sack α * ι £ οη directed. They were attached Eenutsor are dsoiä vorris ^ srtsr * Xsä ^ en of a) atraiiie Soiiiicn'.iür-iö u ^ db) Blondu ^ r or reflection voa the Inneniläolae eggs v / iziusali ^ t ^ oclioibe oäer -platte i ^ usgeseta

^ uO the uS-2atontsc ^ rift 2 739 08D is one parka "süia £ sprinting by 2oIyvIx ^ lGutyralbabnGn eelian & t · you so Parbö consists e ^ ß a Polyvirjy2" butjraihars _e eiaezi Löaun ^ si ^ ittelk and swiööes ₉ S © tcü _e clilorierteii coblei hydrogen or a Wsisisch, - αεΛίθή ₆ cinsn 3? Arl> Dtoif with 2 to 4 cyclical Iterns In Farb ^ toffiiolckül oä & r of a Geoiscä eolGher "^ arbstoife uiid also a Ldsia ^ cj ^ übitel for the ■ of the group of KQtOHQn ₉ Ciiloricrtcü ZoLXenv; ass £ ratoffeii tcid Goaisehoa äör * ^ elboii «! The 1> οΐΐ? θχΐθ £; 2ο Far ^ o has a viscosity of 10 to 5üO Ceütipoiücs * SIäsc Pijrudkea-iöt itir daa Polyviisylbutyraluahnöa braucliya ^ ji sie ^ il) t jeSo dk no Ijös for the fcesonaore der Brfiniü ^ s ^ rtiside lie ^ esde l'röbiefii dor

röflekwierändcn _? liciitdurölilMssisen SGhichtea üüter von Polyvi-nylbutyraX sheets oaer -bahnen «*

■ m creation of a ^ arba for the Esrstölltiia ^ by v; Eiesiö «Uöd licht- _£ "

BATH

The object of the invention is to create Laminates with an intermediate layer of a polyvinyl butyral sheet or film which are an effective heat reflective medium made up of individual metal particles on the printed surface and a light absorbing medium on the opposite surface results «,

This is achieved through the use of a paint that is a liquid medium, one that is soluble in the medium and diffusible dye in the polyvinyl butyral and contains a metal pigment in particulate form »

A particulate metal pigment can expediently be used Aluminum or flaky bronze for use reach.

The transparent laminate according to the invention is characterized in that it has a pair of transparent

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■ visible leaves or webs, with one in between An intermediate layer of thermoplastic material, wherein the intermediate layer on a surface with a "multitude of." individual or separate metal particles is provided and on the opposite surface an effective light-absorbing Medium represented '

The invention is explained in more detail below with the aid of examples. The parts given relate to a weight basis _o

Example 1 to 5

EüS will initially be a blue printing ink that is plasticized Polyvinyl butyral is diffusible by stirring the the following components

Ingredient "'-. Quantity / part by weight

dye

Oil yellow. . '1.31 I.

Eroblau 1.42 ■

Plastp violet. 2.31 "

Medium .

Cyclohexanone 85.00

Butanol 17.00

Polyvinyl butyral 4.25

friäbhyleneglykol- 1.74

di- (2-ethylbutyrate)

109834 / QQIS bath

Powdered aluminum is mixed in equal parts of the aforementioned color in the various amounts given below. The particle size of the aluminum powder is indicated by the fact that 98% by weight of it can pass through a sieve with a mesh size of 0.037 mm which is not made of metal, consists of printed on one side of a number of sheets 0.38 mm thick of plasticized polyvinyl butyral. The printing is done in a rotogravure diaickpreb'ae, the pressure roller of which is etched or grooved in order to give a color gradation effect. Each of the printed sheets. is dusted with sodium bicarbonate on the printed surface, rolled and placed in an oven, which is kept at 85 to 95 ^C for a period of 10 hours, while the color is allowed to diffuse into the sheet. Do. Taking the sheet out of the oven, an examination of the sheets printed with inks containing metal, shows that separated metal particles adhere to the printed surface, while the opposite side shows a well-diffused blue coloration The colored effects also vary in their effect according to the etching or heating of the pressure roller and, according to the original pressure, graduated "

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Each of the sheets is then placed between 3.18 mm thick glass plates and joined to form a plate by subjecting the structure to a uniform pressure of 9.1 kg / cm "at 140 ^° C. for a period of 90 seconds in a letterpress press . The assembly is then placed in a Ölautoklaven and a temperature of 120 to 140 ⁰ C and a pressure of 11, 9-13 »3 kg / cm subjected for a period of 7 minutes.

The transmission and reflection properties of the panels are then examined spectrophotometrically. The following values Λ are obtained from the dark end of the gradation of each panel:

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Table I °

Transmission and reflectance values A, printed surface

Visible 430-70OmM. Infrared 700-1000 m

example Metals in
the colors Si
L. 1 Al powder _o $ 1 9 2 H Il 5g 5 3 Il H Jf ₀ 4th 4th "1096 3 5 (Control
no metal) 10

lU.ma, infrared γυυ-ιυυυ m yes. jo W 'jo D , #. BT

11 65 32 37 42 27 47 22nd

H 3Ö 38 42

74

B ₀ G-opposite surface

Example Visible 430-700 mn. Infrared 700-1000 m η

jo D 2LS 2LS ^ V

1 .9 5 65 14

2 5 ^V 6 37 29

³ ■ ⁴ 6 27 35

5 65 σ \ 37 6th 27 7th 22nd VJl 74

™ 4 3 7 22 38

5 10 5 74 9

Using the table above and especially Part A viewed from it, the values show that the laminates according to the invention an effective heat and light reflective

9 8 3 4/001 p

Have medium at the interface »This is made possible by the Size of reflection shown by Examples 1-4 compared to the reflection obtained from the control example 5 is confirmed. The reflection that .of the Laminates are shown which interlayers with the Inks printed according to the invention contain, is diffuse and no mirror-like reflection, which is not as such from the Table can be found. Part B of Table I shows the effective light absorption at the surface, which is the

printed surface faces, as a result of this surface ^ presented blue staining _e

Example 6

The working method described above is followed again with the Except that the powdered aluminum used for production the metalized colors are replaced by gold as a metal pigment in particle form «,

Upon spectrophotometric examination, the results show Laminate products have an effectiveness in terms of Permeability and reflection, which is analogous to that those made by the corresponding ones made with powdered aluminum Products shown «Slight fluctuations resulting from the choice of metals are the differences

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attributable to the presence of the various metals sindo

Examples 7 to 9

The colors used in the first few examples are again used, with the exception that bronze flakes with a medium Diameter of 1.01 mm and a thickness of 0 | 076 mm can be used instead of the aluminum powder «. The concentration

£: ■■■■■■■■ .. ■■■■■ "■■■■■■ ^:. ■: '-

^ of the bronze flakes used in the colors is below specified

Sheets of polyvinyl butyral 0.38 mm thick are attached to the Knife (0.15 mm knife) coated with the paints that contain the bronze flakes, then dusted and heated to a Induce diffusion of color in the leaf. Plates are made by placing the printed sheets between sheets of glass lays and then formed a laminate at spectrophotometric Testing shows the panels to have the following values

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Table II

Spectrophotometric values Printed surfaces

Example Visible 430-700 mn _o Infrared 700-1000 m Ai «

$ D yR ± _Ώ. '■ - fo R.

8% bronze 2 -32 35 44

flakes ■ "■

32 35 1.8 53 10 71

H $> bronze 4 18 53 25 flakes

$ 1 bronze 5 10 71 15. | flakes

As the above values show, the behavior of the laminate is products are good in terms of heat reflection «.

The inks used in the present invention contain in combination a liquid medium, a dye which is soluble in this liquid medium and diffusible in polyvinyl butyral, and a metal pigment in particle form _{or the like}

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The dyes intended for use are those which 2 to contain 4 cyclic nuclei in the dye molecule. Under cyclic nuclei are aromatic nuclei such as benzene, naphthalene, Anthracene, etc. nuclei and heterocyclic nuclei, such as pyrazolone rings, Understood. Such dyes are examples which are soluble in chlorinated hydrocarbons and ketone solvents such dyes are Ero Blue, Plasto Violet »; Piasto Pink,

1098 34/0015

^'■': -. - 12 ". ■ - '■. ■■■■' ■ '., ■'

Oil-soluble yellow etc. ₀ and various mixtures of these dyes e ₀ The amount of dye used depends on the color and the intensity desired by it "

The colors also contain a small amount of resin. Polyvinyl butyral resins are proposed with a content of "up to 25 io of hydroxyl groups, calculated as polyvinyl alcohol, up to 5 i ° acetate groups, calculated as polyvinyl acetate, the remainder of the resin consisting of polyvinyl butyral. The amount of resin to be used is generally in range between 25 wt und.100 '-.% of the dye,

When the inks are used for printing on plasticized or plasticized polyvinyl butyral resin sheets or sheets for safety glass purposes are determined, it is also proposed that the resin incorporated into the paints contain 20 to 50 parts of plasticizer per 100 parts of polyvinyl butyral resin. The plasticizer should preferably be similar to that used in the sheet to be printed or the corresponding path is already present »Plasticizers that can be used include triethylene glycol di- (2-ethylbutyrate), Dibutyl sebacate, dibutyl cellosolve adipate, and others.

The liquid medium for the paints can be a single solvent or a mixture of solvents for the dye and

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preferably be as for the resin * Individual solvents which can be used are ketones such _o B 'cyclohexanone, in which the dye is soluble. Mixed solvents that can be used include mixtures of alcohols with chlorinated hydrocarbons and ketones and others. Examples of solvent mixtures are: propylene dichloride-butanol, cyclohexanone-butanol, dimethylformamide-xyjol, also acetone or methyl ethyl ketone, methyl isobutyl ketone or the like mixed with butane bl or the like. The type and amount of the solvent to be used depends on its compatibility with the Dye and the resin, and also on its physical properties, such as viscosity and volatility, depending on the particular printing process and the device which is intended for use is limited to be between 10 and 500 cps. In general, the amount of solvent will be between 2000 and 4000 parts per 100 parts of resin present »f

The metal pigments that are used in the practical execution of the Invention can be applied are those which in the visible and infrared parts of the spectrum, reflection devoted these include aluminum, ohrom, gold, silver,

109834/0015

Rhenium, rhodium, titanium or the like, alloys such as bronze and mixtures of the above metals, etc. The metal pigments, which are particulate in nature, are essentially insoluble in the liquid medium of the paint. Preferably the particle size of the metal pigments is in the range from an infinitely small diameter to such an about 2.54 mm ₀ It should, however, one dimension of the particles is less than about 0.127 mm to be. In the case of engraving-like printing, the particle sizes should be such that they adapt to the etchings and corrugations which are engraved in the printing plate or roller, since otherwise larger particles will be wiped off during the printing. Particle sizes of less than 0.076 mm work favorably with this type of printing. When coating with a knife or squeegee, particles of larger shape can be adjusted more easily. The amount of metallic pigment that is used in a given color depends on the amount required to achieve the desired heat reflection in a given laminate achieve. In order to keep the pigment in color, anti-flocculation agents or spreading agents can be used, and various printing aids such as wetting agents can be incorporated.

The colors can be mixed in any of the usual ways be ,, The direct mixing of the metal pigments with

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the dye solution is perhaps the simplest way of working, and she works well.

The pigments can be added directly to the dye solution, or they can be added together with part of the liquid medium. When the latter procedure is carried out, this proportion of the liquid can be used to introduce auxiliary substances such as Z ₀ B ₀ anti-flocculants or the like into the paint. ,

In the production of intermediate layers of transparent plates, such as are _o B ₀ in windshields od _or the like. Go to the application that is the intermediate layer material preferably consists of a web, a sheet or a film of plasticized or unplasticized polyvinyl ,, The latter has the same constituent composition such as the polyvinyl butyral resin, which has previously been specified for incorporation into the paint in small proportions, ie it can contain up to 25 ? ° hydroxyl groups, calculated as polyvinyl alcohol, up to 3 $ acetate groups, calculated as polyvinyl acetate, the remainder of the resin being polyvinyl butyral. However, the inks can be successfully printed onto other polyvinyl acetates as well as other thermoplastic materials.

109834/0015

When polyvinyl butyral interlayers are printed with the listed colors and the dye is allowed to diffuse, the area on which the dye has been printed shows a metallic surface with a patterned appearance, which is represented by separate metallic pigment particles deposited on it , has been obtained »The surface is due to a highly diffuse reflection from both of. radiated heat as well as radiated light, whereby the reflection differs from mirror-like reflection «. Accordingly, the glare is even considerably from that reduced to that surface, which is shown solid, metallized surfaces, which are the result of a Yakuumniederschlagung, _o Further, on the surface opposite to the printed, the surface glare effective by the provision of a light absorbing Medium reduced to a minimum. In this manner, intermediate layers of the invention are printed with the colors in accordance with, layers between the carrier set "or be coated with these, for example with glass or other transparent materials, for example, synthetic materials, including PoIymethylmethacrylat, polyethylene, polypropylene od _e etc. _o, are layered so that plates can be achieved, which is when installed in vehicles, buildings or the like od _{0 0,} where the metallized surface wärmere- inflected outwardly directed, characterized by a minimum transmittance radiant heat "

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In connection with this, light from secondary sources, which occurs on the inwardly facing surface of the laminates, is reduced. These two punctures contribute to the comfort of the occupants of the vehicles or the residents of the buildings «. Finally, since the matallisierte surface is formed of particulate pigment, the glare, which is usually reflected by metallized films is vermiedeni ₀ These properties make in practice the invention, particularly in the production of windshields for automobiles, industrial water (| bar "runt only the windshields manufactured in this way contribute to the comfort and safety of the driver or the occupants of the vehicle in which they are installed, but this result is achieved without undue disturbance to the safety of others and especially the drivers of others Vehicles achieved by producing less mirror-like glare or mirror-like glare that they have to come to terms with «

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Claims (1)

Claims 1 'Transparent' laminate characterized in that it comprises a pair of transparent sheets or webs with an intermediate layer of thermoplastic material therebetween, the intermediate layer being provided on one surface with a plurality of individual metal particles and on the opposite surface thereof an effective light-absorbing one Medium represents. . Λ ^ν 2 * Laminate according to claim 1, characterized in that that the metal consists of particulate aluminum. 3. Laminate according to claim 1, characterized in that the metal is made of flaky bronze. 1098 3 4/0015 BATH ORIGINAL